Sustainable Starch/Lignin Nanoparticle Composites Biofilms for Food Packaging Applications.

Construction of sustainable composite biofilms from natural biopolymers are greatly promising for advanced packaging applications due to their biodegradable, biocompatible, and renewable properties. In this work, sustainable advanced food packaging films are developed by incorporating lignin nanoparticles (LNPs) as green nanofillers to starch films. This seamless combination of bio-nanofiller with biopolymer matrix is enabled by the uniform size of nanofillers and the strong interfacial hydrogen bonding. As a result, the as-prepared biocomposites exhibit enhanced mechanical properties, thermal stability, and antioxidant activity. Moreover, they also present outstanding ultraviolet (UV) irradiation shielding performance. As a proof of concept in the application of food packaging, we evaluate the effect of composite films on delaying oxidative deterioration of soybean oil. The results indicate our composite film could significantly decrease peroxide value (POV), saponification value (SV), and acid value (AV) to delay oxidation of soybean oil during storage. Overall, this work provides a simple and effective method for the preparation of starch-based films with enhanced antioxidant and barrier properties for advanced food packaging applications.

Bioinspired Stabilization of Amorphous Calcium Carbonate by Carboxylated Nanocellulose Enables Mechanically Robust, Healable, and Sensing Biocomposites.

Nature builds numerous structurally complex composites with fascinating mechanical robustness and functionalities by harnessing biopolymers and amorphous calcium carbonate (ACC). The key to successfully mimicking these natural designs is efficiently stabilizing ACC, but developing highly efficient, biodegradable, biocompatible, and sustainable stabilizing agents remains a grand challenge since anhydrous ACC is inherently unstable toward crystallization in the wet state. Inspired by the stabilized ACC in crustacean cuticles, we report the efficient stabilization ability of the most abundant biopolymer-cellulose nanofibrils (CNFs) for ACC. Through the cooperative stabilizing effect of surface carboxyl groups and a rigid segregated network, the CNFs exhibit long-term stability (more than one month) and achieved a stabilization efficiency of 3.6 and 4.4 times that of carboxymethyl cellulose (CMC) and alginate, respectively, even higher than poly(acrylic acid). The resulting CNF/ACC dispersions can be constructed into transparent composite films with the high strength of 286 MPa and toughness up to 28.5 MJ/m3, which surpass those of the so far reported synthetic biopolymer-calcium carbonate/phosphate composites. The dynamic interfacial interaction between nanocomponents also provides the composite films with good self-healing properties. Owing to their good wet stability, the composite films present high humidity sensitivity for monitoring respiration and finger contact.

Acidic deep eutectic solvent assisted mechanochemical delignification of lignocellulosic biomass at room temperature.

Lignocellulosic biomass is the most abundant natural polymer on Earth, but the efficient fractionation and refinery of all its components remain challenging. Acidic deep eutectic solvents refining is a promising method, while it is likely to cause lignin condensation and carbohydrates degradation, especially at server operation conditions. Here we propose the use of acidic deep eutectic solvent (DES), choline chloride/p-toluenesulfonic acid assisted mechanochemical pretreatment (DM) for efficient lignocellulose fractionation at mild condition. Four representative lignocellulose, wheat straw, moso bamboo, poplar wood and pine wood were selected at varied milling time (3, 6 h) to assess the fractionation ability of this strategy. This DM pretreatment demonstrated a rather high cellulose retentions (∼90 %) and extent of delignification for wheat straw and bamboo biomass, which corresponds to a high extent of enzymatic hydrolysis (∼75.5 %) for sugar platform pursuing. The extracted lignin showed rather high content of ß-O-4' leakages due to the swelling effect of deep eutectic solvent and mild operation conditions. This work provided a promising strategy to fractionate lignocellulose using deep eutectic solvents with the goal of simultaneous cellulose hydrolysis and reactive lignin obtaining that is usually difficult to realize using traditional chemical fractionation approach.

Melt-processed poly (vinyl alcohol)/corn starch/nanocellulose composites with improved mechanical properties.

Corn starch (CS) and cellulose nanofibrils (CNFs) were incorporated into biodegradable poly (vinyl alcohol) (PVA) to prepare mechanically robust and sustainable composites through melt-processing. Based on the regulation and control of hydrogen bonding network, CS and CNFs can extend the processing window and improve the thermoplasticity of PVA composites. Fourier transform infrared spectroscopy and Raman spectra analysis indicate that the intra- and inter-molecular hydrogen bonds of PVA are broken, accompanied by the formation of new hydrogen bonds among PVA, CS and CNFs during the melt-processing treatment. Thermal analysis shows that the processing window of PVA composite is significantly broadened to 131.46 °C. The tensile strength, modulus and elongation at break of the composites reach to 28.19 MPa, 1572.54 MPa and 10.72% by the incorporation of 10 wt% CS and 10 wt% CNFs. This strategy is not only expected to provide a direction for preparing complex three-dimensional products of PVA by melt-processing, but also provide a method to enhance the mechanical properties of other biodegradable plastics.

Homogeneous synthesis of Ag nanoparticles-doped water-soluble cellulose acetate for versatile applications.

We report a facile and efficient approach for synthesis of well-dispersed and stable silver nanoparticles (Ag NPs) using water-soluble cellulose acetate (CA) as both reductant and stabilizer. Partially substituted CA with highly active hydroxyl groups and excellent water-solubility is able to reduce silver ions in homogeneous aqueous medium effectively. The synthesized Ag NPs were characterized by UV-vis spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and energy dispersive X-ray spectroscope analysis. The as-prepared Ag NPs were well-dispersed, showing a surface plasmon resonance peak at 426nm. The resulted Ag NPs@CA nanohybrids exhibit high catalytic activity for the reduction of 4-nitrophenol to 4-aminophenol in the presence of NaBH4. Meanwhile, the nanohybrids are also effective in inhibiting the growth of bacterial. This environmentally friendly method promotes the use of renewable natural resources to prepare a variety of inorganic-organic materials for catalysis, antibacterial, sensors and other applications.

Water-soluble cellulose acetate from waste cotton fabrics and the aqueous processing of all-cellulose composites.

The objective of this study is to explore the possibility of using waste cotton fabrics (WCFs) as low cost feedstock for the production of value-added products. Our previous study (Tian et al., 2014) demonstrated that acidic ionic liquids (ILs) can be highly efficient catalysts for controllable synthesis of cellulose acetate (CA) due to their dual function of swelling and catalyzing. In this study, an optimized "quasi-homogeneous" process which required a small amount of acidic ILs as catalyst was developed to synthesize water-soluble CA from WCFs. The process was optimized by varying the amounts of ILs and the reaction time. The highest conversion of water-soluble CA from WCFs reached 90.8%. The structure of the obtained water-soluble CA was characterized and compared with the original WCFs. Moreover, we demonstrate for the first time that fully bio-based and transparent all-cellulose composites can be fabricated by simple aqueous blending of the obtained water-soluble CA and two kinds of nanocelluloses (cellulose nanocrystals and cellulose nanofibrils), which is attractive for the applications in disposable packaging materials, sheet coating and binders, etc.

Melt-processed poly(vinyl alcohol) composites filled with microcrystalline cellulose from waste cotton fabrics.

Waste cotton fabrics (WCFs), which are generated in a large volume from the textile industry, have caused serious disposal problem. Recycling WCFs into value-added products is one of the vital measures for both environmental and economic benefits. In this study, microcrystalline cellulose (MCC) was prepared by acid hydrolysis of WCFs, and used as reinforcement for melt-processed poly(vinyl alcohol) (PVA) with water and formamide as plasticizer. The microstructure and mechanical properties of the melt-processed PVA/MCC composites were characterized by Fourier transform infrared spectra, Raman spectra, differential scanning calorimetry, thermal gravimetric analysis, X-ray diffraction, tensile tests and dynamic mechanical analysis. The results indicated that MCC could establish strong interfacial interaction with PVA through hydrogen bonding. As a result, the crystallization of PVA was confined and its melting temperature was decreased, which was beneficial for the melt-processing of PVA. Compared with the unfilled PVA, the PVA/MCC composites exhibited remarkable improvement in modulus and tensile strength.

Acetone-soluble cellulose acetate extracted from waste blended fabrics via ionic liquid catalyzed acetylation.

Isolation of cellulose from waste polyester/cotton blended fabrics (WBFs) is a bottleneck for recycling and exploiting waste textiles. The objective of this study was to provide a new environmental-friendly and efficient approach for extracting cellulose derivatives and polyester from WBFs. A Bronsted acidic ionic liquid (IL) N-methyl-imidazolium bisulfate, [Hmim]HSO4, was used as a novel catalyst for acetylation of cellulose rather than a solvent with the aim to overcome low isolation efficiency associated with the very high viscosity and relatively high costs of ILs. The extraction yield of acetone-soluble cellulose acetate (CA) was 49.3%, which corresponded to a conversion of 84.5% of the cellulose in the original WBFs; meanwhile, 96.2% of the original poly(ethylene terephthalate) (PET) was recovered. The extracted CA was characterized by (1)H NMR, FTIR, XRD and TGA analysis, and the results indicated that high purity acetone-soluble CA and carbohydrate-free PET could be isolated in this manner from WBFs.